KR940010094B1 - Concrete admixture - Google Patents

Concrete admixture Download PDF

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KR940010094B1
KR940010094B1 KR1019870008311A KR870008311A KR940010094B1 KR 940010094 B1 KR940010094 B1 KR 940010094B1 KR 1019870008311 A KR1019870008311 A KR 1019870008311A KR 870008311 A KR870008311 A KR 870008311A KR 940010094 B1 KR940010094 B1 KR 940010094B1
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히데오 야기
도루 다께우찌
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후지사와야꾸힝고교 가부시끼가이샤
후지사와 도모끼찌로
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/304—Air-entrainers

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Abstract

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Description

콘크리트 혼화제Concrete admixture

본 발명은 프레쉬(fresh)콘크리트 제조시 그의 유동성 및 공기 연행성을 적당한 수준으로 유지시키는데 사용하기 위한 콘크리트 혼화제에 관한 것이다.The present invention relates to concrete admixtures for use in maintaining fresh fluidity and air embrittlement at moderate levels in the production of fresh concrete.

프레쉬콘크리트의 유동성을 증가시키기 위해 사용되는 화합물 중 하기 일반식 (A-1)의 화합물 10-95 중량부 및 하기 일반식 (A-2)의 화합물 또는 그의 염 90-5중량부를 중합시켜 제조한 공중합체가 알려져 있다.Prepared by polymerizing 10-95 parts by weight of the compound of the following general formula (A-1) and 90-5 parts by weight of the compound of the following general formula (A-2) or salts thereof Copolymers are known.

Figure kpo00001
Figure kpo00001

상기 식들 중, R1은 수소 또는 메틸이고, R2는 저급(C2-C4)알킬렌이며, R3는 수소 또는 저급(C1-C5)알킬이고, 정수 1-100이며, R4는 수소 또는 메틸이다. 이와 같은 공중합체(이하"공중합체 X "라 칭함)는 일본국 특허 공고 제 59-18338호에 기재되어 있다.Wherein R 1 is hydrogen or methyl, R 2 is lower (C 2 -C 4 ) alkylene, R 3 is hydrogen or lower (C 1 -C 5 ) alkyl, integer 1-100, R 4 is hydrogen or methyl. Such copolymers (hereinafter referred to as "copolymer X") are described in Japanese Patent Publication No. 59-18338.

다음에 기재된 바와 같이, 상기 공중합체를 프레쉬 콘크리트에 첨가할 경우 한편으로 콘크리트의 유동성이 개선되고, 다른 한편으로 생성된 콘크리트에 거친 기공 또는 기포를 형성시키는 다량의 공기가 연행되며, 그리하여 생성된 콘크리트의 강도가 저하되고, 동결 융해 저항성이 현저하게 감소되는 부적합한 결과가 초래된다.As described below, when the copolymer is added to the fresh concrete, the fluidity of the concrete is improved on the one hand, and on the other hand, a large amount of air is entrained to form coarse pores or bubbles in the resulting concrete, and thus the concrete produced This results in inadequate results in that the strength of and the freeze-thaw resistance are significantly reduced.

본 발명자들은 상기 문제점들을 해결하기 위하여 연구한 결과 상기 정의된 공중합체 로 되는 성분, 하기 일반식(B)The present inventors have studied to solve the above problems, the component consisting of the copolymer defined above, the following general formula (B)

Figure kpo00002
Figure kpo00002

(식중, R5는 수소 또는 알카노일이고, R6는 수소 또는 알킬이고, m은 정수 1-99이고 n은 정수 1-15이되 단, m+n이 정수 2-100이며Wherein R 5 is hydrogen or alkanoyl, R 6 is hydrogen or alkyl, m is an integer from 1-99 and n is an integer from 1-15, with m + n being an integer from 2-100

Figure kpo00003
Figure kpo00003

의 단위가 임의로 나타남)의 화합물로 되는 B성분 및 폴리옥시에틸렌 알킬 에테르 술페이트 또는 폴리옥시에틸렌 알킬페닐 에테르 술페이트 또는 그의 염, 폴리옥시에틸렌 알킬 에테르 포스페이트 또는 폴리옥시에틸렌 알킬페닐 에테르 포스페이트 또는 그의 염 및 알킬벤젠술폰산 또는 그의 염으로 되는 군 중에서 선택된 적어도 하나의 화합물로 되는 C성분을 프레쉬 콘크리트에 첨가할 경우, 프레쉬 콘크리트의 유동성이 증가될 수 있으며 동시에 공기가 연행될 수 있으며 적합한 크기의 기포가 형성되며 그 결과 강도 및 동결 융해 저항성이 우수한 콘크리트 구조물을 얻을 수 있음을 발견하였다. 본 발명은 상기 발견에 기초하여 완성되었다.Is a compound of B) and polyoxyethylene alkyl ether sulfate or polyoxyethylene alkylphenyl ether sulfate or salt thereof, polyoxyethylene alkyl ether phosphate or polyoxyethylene alkylphenyl ether phosphate or salt thereof And C component comprising at least one compound selected from the group consisting of alkylbenzenesulfonic acid or salts thereof to the fresh concrete, the fluidity of the fresh concrete can be increased and at the same time air can be entrained and bubbles of suitable size are formed. As a result, it was found that a concrete structure having excellent strength and freeze-thawing resistance can be obtained. The present invention has been completed based on the above findings.

본 발명에 의한 콘크리트 혼합물을 사용할 수 있는 콘크리트에는 기본적으로 시멘트, 물, 골재 및 콘크리트 단위 용적당 물의 양을 감소시키기 위하여 임의로 첨가된 적합한 감수제(減水劑)로 되는 프레쉬 콘크리트 모두가 포함된다.Concretes which can use the concrete mixtures according to the present invention basically include both cement, water, aggregates and fresh concrete which is optionally added a suitable water reducing agent to reduce the amount of water per unit volume of concrete.

시멘트의 예로서 통상의 시판용 포틀랜드 시멘트, 조강(早强) 시멘트, 중용열(中庸熱)시멘트, 고로(高爐)슬래그시멘트, 플라이 에쉬(fly ash) 시멘트 및 추가로 플라이 에쉬, 과립상 슬래그 분말, 규산질 혼화제등으로 부분적으로 대치시킨 상기 시멘트를 들 수 있다.Examples of cements include conventional commercial portland cement, crude steel cement, medium heat cement, blast furnace slag cement, fly ash cement and additionally fly ash, granular slag powder, And the cement partially replaced with a siliceous admixture.

골재에는 모래와 같은 잔골재 및 자갈(gravel), 소석(pebbles), 쇄석(crusked stone)등과 같은 굵은 골재가 포함된다.Aggregates include fine aggregates such as sand and coarse aggregates such as gravels, pebbles, crushed stones, and the like.

R2로 나타낸 저급 알킬렌에는 2-4개의 탄소 원자를 갖는 저급 알킬렌이 포함되며 그 예로서 적합한 것은 에틸렌, 메틸 에틸렌, 디메틸에틸렌 등이다.Lower alkylene represented by R 2 includes lower alkylene having 2-4 carbon atoms and suitable examples thereof are ethylene, methyl ethylene, dimethylethylene and the like.

R3로 나타낸 저급 알킬에는 1-5개의 탄소 원자를 갖는 저급 알킬이 포함되며 그 예로서 적합한 것은 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, 펜틸, 이소펜틸 등이다.Lower alkyl represented by R 3 includes lower alkyl having 1-5 carbon atoms and suitable examples thereof are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl and the like.

정수 ι은 1-25가 적합하다.The integer ι is 1-25.

R5로 나타낸 알카노일에는 1-30개, 적합하기로는 12-24개의 탄소 원자를 갖는 알카노일이 포함되며, 그 예로서 적합한 것은 도데카노일, 트리데카노일, 테트라데카노일, 펜타데카노일, 헥사데카노일, 헵타데카노일, 옥타데카노일, 노나데카노일, 이코사노일, 헤니코사노일, 도코사노일, 트리코사노일, 테트라코사노일등이다.Alkanoyl represented by R 5 includes alkanoyl having 1-30, suitably 12-24 carbon atoms, examples of which are dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, Hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, icosanoyl, henicosanoyl, docosanoyl, tricosanoyl, tetracosanoyl and the like.

R6로 나타낸 알킬에는 1-30개, 적합하기로는 12-24개의 탄소 원자를 갖는 알킬이 포함되며 그 예로서 적합한 것은 도데실, 트리데실, 테트라데실, 펜타데실, 헥사데실, 옥타데실, 노나데실, 이코실, 헤니코실, 도코실, 트리코실, 테트라코실 등이다.Alkyl represented by R 6 includes alkyl having 1-30, suitably 12-24 carbon atoms, examples of which are dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nona Decyl, ecosil, henicosil, docosyl, tricosyl, tetracosyl and the like.

정수 m 및 n은 각각 10-60이되 단, m+n은 12-66이 적합하다.The integers m and n are each 10-60, but m + n is preferably 12-66.

공중합체 X의 분자량은 500-50,000, 적합하기로는 10,000-30,000이다The molecular weight of copolymer X is 500-50,000, suitably 10,000-30,000.

C성분에 있어서, 폴리옥시에틸렌 알킬 에테르 술페이트 및 폴리옥시에틸렌 알킬페닐 에테르 술페이트는 다음 일반식 (C-1)로 표시될 수 있다. 즉,In the C component, polyoxyethylene alkyl ether sulfate and polyoxyethylene alkylphenyl ether sulfate can be represented by the following general formula (C-1). In other words,

Ra-O-(CH2CH2O)naSO3H (C-1)Ra-O- (CH 2 CH 2 O) naSO 3 H (C-1)

상기 식중, Ra는 5-20개의 탄소 원자를 갖는 알킬이거나 5-20개 탄소 원자를 갖는 알킬로 치환된 페닐이고, na는 정수 1-10이다.Wherein Ra is phenyl substituted with alkyl having 5-20 carbon atoms or substituted with alkyl having 5-20 carbon atoms and na is an integer 1-10.

상기 일반식(C-1)에 있어서, Ra로 나타낸 알킬은 8-15개의 탄소 원자를 갖는 알킬이거나 8-15개의 탄소 원자를 갖는 알킬이거나 8-15개의 탄소 원자를 갖는 알킬로 치환된 페닐이며 그 예로서 적합한 것은 옥틸, 노닐, 데실, 운데실, 도데실, 트리페실, 테트라데실페닐, 펜타데실페닐등이다.In the above general formula (C-1), alkyl represented by Ra is alkyl having 8-15 carbon atoms, alkyl having 8-15 carbon atoms, or phenyl substituted with alkyl having 8-15 carbon atoms. Suitable examples are octyl, nonyl, decyl, undecyl, dodecyl, tripecyl, tetradecylphenyl, pentadecylphenyl and the like.

정수na는 2-5가 적합하다.The integer na is suitable for 2-5.

화합물(C-1)의 염에는 알칼리 금속염(예, 나트륨염, 칼륨염 등), 알칼리 토금속염(예, 칼슘염, 마그네슘염 등), 암모늄염, 에탄올아민염(모노에탄올아민염, 디에탄올아민염 및 트리에탄올아민염 등)등과 같은 무기염 및 유기염이 포함되며 그 예로서 에탄올아민염이 적합하며 트리에탄올아민염이 가장 적합하다.Salts of the compound (C-1) include alkali metal salts (eg, sodium salts, potassium salts, etc.), alkaline earth metal salts (eg, calcium salts, magnesium salts, etc.), ammonium salts, ethanolamine salts (monoethanolamine salts, diethanolamines). Inorganic salts and organic salts such as salts and triethanolamine salts, etc.), and ethanolamine salts are suitable as examples, and triethanolamine salts are most suitable.

폴리옥시에틸렌 알킬 에테르 포스페이트 및 폴리옥시에틸렌 알킬페닐 에테르 포스페이트는 하기 일반식으로 나타낼 수 있다. 즉,Polyoxyethylene alkyl ether phosphate and polyoxyethylene alkylphenyl ether phosphate can be represented by the following general formula. In other words,

Figure kpo00004
Figure kpo00004

식중, Rb 1은 구조식 Rb 4-O-(CH2CH2O)nb-(여기서, Rb 4는 4-18개의 탄소 원자를 알킬이거나 4-18개의 탄소 원자를 갖는 알킬로 치환된 페닐이고, nb는 정수 1-15임)의 기이고, Rb 2및 Rb 3는 각각 히드록시 또는 구조식 Rb 4-O-(CH2CH2O)nb-(여기서, Rb 4및 nb는 상기 정의한 바와 같음)의 기이다.Wherein R b 1 is the structural formula R b 4 -O- (CH 2 CH 2 O) nb- (wherein R b 4 is substituted with 4-18 carbon atoms alkyl or alkyl having 4-18 carbon atoms Phenyl, nb is an integer of 1-15, and R b 2 and R b 3 are each hydroxy or the formula R b 4 —O— (CH 2 CH 2 O) nb—, wherein R b 4 and nb is the same as defined above).

Rb 4로 나타낸 알킬은 6-12개의 탄소 원자를 갖는 알킬이거나 6-12개의 탄소 원자를 갖는 알킬로 치환된 페닐이 적합하며 그 예로서 적합한 것은 헥실, 헵틸, 옥틸, 노닐, 데실, 운데실, 도데실, 헥실페닐, 헵틸페닐, 옥틸페닐, 노닐페닐, 데실페닐,운데실페닐, 도데실페닐 등이다.Alkyl represented by R b 4 is suitably phenyl substituted with alkyl having 6-12 carbon atoms or substituted with alkyl having 6-12 carbon atoms, examples of which are hexyl, heptyl, octyl, nonyl, decyl, undecyl , Dodecyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl and the like.

정수 nb는 2-10이 적합하다.The integer nb is suitable for 2-10.

화합물 (C-2)의 염으로서 화합물 (C-1)의 염으로 예시한 것과 같은 염을 들 수 있으며, 이들 중 나트륨염 및 에탄올아민염이 적합하다.As a salt of a compound (C-2), the same salt as what was illustrated by the salt of a compound (C-1) is mentioned, Among these, sodium salt and ethanolamine salt are suitable.

알킬벤젠술폰산은 하기 일반식으로 표시된다. 즉,Alkylbenzenesulfonic acid is represented by the following general formula. In other words,

Figure kpo00005
Figure kpo00005

상기 식중, Rb 1은 8-20개의 탄소 원자를 갖는 알킬이다.Wherein R b 1 is alkyl having 8-20 carbon atoms.

상기 식에서 Rb 1으로 나타낸 알킬은 10-15개의 탄소 원자를 갖는 알킬이며 그의 예로서 적합한 것은 데실, 운데실, 도데실, 테트라데실, 펜타데실 등이다.Alkyl represented by R b 1 in the above formula is alkyl having 10-15 carbon atoms and suitable examples thereof are decyl, undecyl, dodecyl, tetradecyl, pentadecyl and the like.

화합물 (C-3)의 염으로서, 화합물(C-1)의 염으로 예시한 것과 같은 염을 들 수 있으며, 이들 중 나트륨염이 적합하다.As a salt of a compound (C-3), the salt similar to what was illustrated by the salt of a compound (C-1) is mentioned, Among these, a sodium salt is suitable.

성분 A,B 및 C의 혼합비는 프레쉬 콘크리트 성분(시멘트, 물 및 골재)의 비율 및 (또는) 감수제의 존재 또는 부재에 의존하여 변화하지만, 성분 A가90-95 중량부, 성분 B가 0.05-5중량부이고 성분 C가 0.01-10중량부인 것이 적합하다.The mixing ratio of components A, B and C varies depending on the ratio of fresh concrete components (cement, water and aggregate) and (or) the presence or absence of a water reducing agent, but component A is 90-95 parts by weight and component B is 0.05- 5 parts by weight and component C of 0.01-10 parts by weight are suitable.

이와 같이 얻어진 콘크리트 혼화제는 일반적으로 시멘트에 대하여 0.001-1.0중량%(이하"X"는 항상 중량%를 의미함), 적합하기로는 0.001-0.2%로 프레쉬 콘크리트에 첨가된다. 그러나, 상기 첨가량은 프레쉬 콘크리트의 목적하는 유동성, 성분비, 감수제의 존재 또는 부재 및 (또는) 첨가 시간에 의존하여 변화한다.The concrete admixture thus obtained is generally added to the fresh concrete at 0.001-1.0% by weight (hereinafter "X" always means% by weight) relative to cement, suitably 0.001-0.2%. However, the amount of addition varies depending on the desired fluidity of the fresh concrete, the component ratio, the presence or absence of a reducing agent and / or the addition time.

본 발명에 의한 콘크리트 혼화제는 통상의 방법에 의하여 프레쉬 콘크리트에 첨가된다. 그리하여, 이 혼화제는 콘크리트 혼합시 혼합수에 또는 일단 혼합된 프레쉬 콘크리트에 첨가될 수 있다. 또한, 이 혼화제는 프레쉬 콘크리트가 콘크리트 혼합 트럭에 의하여 건축현장에 도착한 후 프레쉬 콘크리트에 첨가될 수 있다.The concrete admixture according to the present invention is added to the fresh concrete by conventional methods. Thus, this admixture can be added to the mixed water in mixing the concrete or to the fresh concrete once mixed. This admixture may also be added to the fresh concrete after the fresh concrete arrives at the construction site by the concrete mixing truck.

본 발명에 의한 콘크리트 혼화제를 프레쉬 콘크리트에 첨가할 경우 적당한 수준의 유동성 및 공기 연행성이 유지되지만 공중합체 X만을 사용할 경우와 같이 다량의 거친 기포가 연행되지 않으며 그리하여 생성된 콘크리트의 강도 또는 동결 융해 저항성이 현저하게 감소되지 않는다.When the concrete admixture according to the present invention is added to the fresh concrete, an appropriate level of fluidity and air entrainment are maintained, but a large amount of coarse bubbles are not entrained, as in the case of using only copolymer X, and thus the strength or freeze-thawing resistance of the concrete produced. This is not significantly reduced.

본 발명의 효과를 설명하기 위하여 본 발명에 의한 콘크리트 혼화제를 첨가하여 제조한 콘크리트의 동결 융해 시험 데이타를 얻었다.In order to explain the effect of the present invention, freeze-thawing test data of concrete prepared by adding the concrete admixture according to the present invention was obtained.

시험 : 콘크리트의 동결 융해 시험Test: Freeze-thawing test of concrete

(1) 시험방법:(1) Test method:

i) 콘크리트 시험체의 제조 방법.i) method of making concrete specimens.

20°±2℃의 시험실내에서, 50ι 가경식(可傾式, tilting) 혼합기를 굵은 골재(이하 "G"로 칭함), 반량의 잔골재(이하"S"로 칭함), 시멘트(이하"C"로 칭함), 반량(나머지)의 S 및 필요에 따라서 감수제 및 피시험 콘크리트 혼화제를 이루는 C성분의 일부로 계속해서 채우고 이어서, 동시 첨가일 경우 콘크리트 혼화제의 나머지 성분을 함유하는 몰(이하 "W"로 칭함)을 첨가하였다. 이어서, 3분 동안 혼합하여 프레쉬 콘크리트를 얻었다.In a laboratory at 20 ° ± 2 ° C, a 50ι tilting mixer is coarse aggregate (hereinafter referred to as "G"), half the fine aggregate (hereinafter referred to as "S"), and cement (hereinafter referred to as "C"). "," Half (S) of S and the moles containing the remaining components of the concrete admixture (hereinafter "W"), if necessary, continuing to be filled with a portion of the C component which forms the water reducing agent and the concrete admixture under test, if necessary. Is called). This was followed by mixing for 3 minutes to obtain fresh concrete.

시차 첨가 방법을 행할 경우, 물을 채우고 30초 동안 혼합시킨 후 피시험 콘크리트 혼화제 성분을 첨가하였다. 이어서, 2.5분 동안 혼합시켜 프레쉬 콘크리트를 얻었다.When performing the differential addition method, water was added and mixed for 30 seconds, and then the concrete admixture component under test was added. Then it was mixed for 2.5 minutes to obtain fresh concrete.

이와 같이 얻어진 프레쉬 콘크리트를 콘크리트시험체 제조용 거푸집 (10cm × 10cm ×40cm) 에 넣고 경화시켜 동결 융해 시험용 콘크리트 시험체를 얻었다.The fresh concrete thus obtained was placed in a mold for producing a concrete test body (10 cm x 10 cm x 40 cm) and cured to obtain a concrete test body for freeze-thawing test.

사용된 재료:Material used:

C : 통상의 포틀랜드 시멘트(비중 3.16)C: ordinary Portland cement (specific gravity 3.16)

S : 강모래(비중 2.63, FM(조립율) 2.71)S: strong sand (specific gravity 2.63, FM 2.71)

G : 쇄석 (비중 2.67, FM 6.70)G: Crushed stone (weight 2.67, FM 6.70)

ii) 콘크리트 배합ii) concrete mix

콘크리트 배합율 표 1에 나타내었다.Concrete mixing ratio is shown in Table 1.

[표 1] 콘크리트 배합[Table 1] Concrete Mixing

Figure kpo00006
Figure kpo00006

(s/a: 모래-굵은 골재의 비)(s / a: ratio of sand to coarse aggregate)

iii) 시험 성분 :iii) Test Component:

A 성분 :A ingredient:

일반식(-1)의 화합물(여기서, R1및 R2는 각각 메틸이고, R2는 에틸렌이며 ℓ은 9임) 40중량부 및 일반식 (-2)의 화합물 (여기서, R4는 메틸임) 60중량부를 중합시켜 제조한 것으로서 분자량이 약 20,000이고 그의 40% 수용액의 점도가 200cps인 나트륨염 형태의 공중합체.40 parts by weight of a compound of formula (-1), wherein R 1 and R 2 are each methyl, R 2 is ethylene and l is 9; and a compound of formula (-2), wherein R 4 is methyl The sodium salt copolymer having a molecular weight of about 20,000 and a viscosity of 200cps of a 40% aqueous solution thereof.

B 성분 :B component:

일반식(B)의 화합물(여기서, R5는 스테아로일, R6는 수소, m은 35이고 은 5임).A compound of formula (B) wherein R 5 is stearoyl, R 6 is hydrogen, m is 35 and silver 5.

분자량 : 약 2,500Molecular weight: about 2,500

C성분 :C ingredient:

C-: 도데실 벤젠술폰산 나트륨.C-: sodium dodecyl benzenesulfonate.

C-B : 에탄올아민염 형태의 일반식 (C-2)의 화합물(여기서, Rb 1및 Rb 2는 각각CB: A compound of the general formula (C-2) in the form of an ethanolamine salt, wherein R b 1 and R b 2 are

Figure kpo00007
Figure kpo00007

이고, Rb 3는 히드록시임) 및 에탄올아민염 형태의 일반식(C-2)의 화합물(여기서, Rb 1은R b 3 is hydroxy) and a compound of formula (C-2) in the form of an ethanolamine salt, wherein R b 1 is

Figure kpo00008
Figure kpo00008

이고, Rb 2및 Rb 3는 각각 히드록시임)의 동량 혼합물.And R b 2 and R b 3 are each hydroxy.

C-C:C-C:

Figure kpo00009
Figure kpo00009

감수제 :Reducing Agent:

D-

Figure kpo00010
: 리그닌술폰산칼슘 :D-
Figure kpo00010
Calcium lignin sulfonate

D-B : 소듐 글루코네이트D-B: Sodium Gluconate

콘크리트 시험 방법 :Concrete test method:

슬럼프(slump)시험 : JIS A 1101법.Slump test: JIS A 1101 method.

공기 함량 측정 : JIS A 1128법.Air content measurement: JIS A 1128 method.

동결 융해 저항성 시험 :Freeze thaw resistance test:

콘크리트 시험체를 2주동안 수중양생(20℃)시킨 후, JIS A 6204법에 의하여 시험을 행하였다. 기포 간격 계수를 ASTM C457-82에 기재된 바와 같이 선형 트래버스(traverse)법에 의하여 측정하였다.The concrete test body was cured under water (20 ° C) for 2 weeks, and then tested by JIS A 6204 method. Bubble spacing coefficients were measured by linear traverse method as described in ASTM C457-82.

(2) 시험 결과:(2) test result:

얻어진 시험 결과를 표 2 및 3에 나타내었다.The test results obtained are shown in Tables 2 and 3.

[표 2] 콘크리트 배합[Table 2] Concrete Mixing

Figure kpo00011
Figure kpo00011

WRA : 감수제WRA: Reducing Agent

[표 3] 결과Table 3 Results

Figure kpo00012
Figure kpo00012

상기 표 3에 명백하게 나타난 바와 같이, 프레쉬 콘크리트의 유동성을 증가시키기 위하여 성분만을 첨가할 경우, 생성된 콘크리트의 동결 융해 저항성이 현저하게 감소되며 콘크리트는 200회의 동결 융해 사이클후의 상대적 당탄성 계수가 적어도 80%이어야 하는 일반적인 필수 조건을 충족시키지 못한다. 이와 반대로, 본 발명에 의한 콘크리트 혼화제를 첨가할 경우, 감수제의 병용과 관계없이 동결융해 저항성이 전혀 감소되지 않는다.As is apparent from Table 3 above, when only components are added to increase the flowability of fresh concrete, the freeze-thaw resistance of the resulting concrete is significantly reduced and the concrete has a relative sugar modulus of at least 80 after 200 freeze-thaw cycles. It does not meet the general prerequisites to be%. On the contrary, when the concrete admixture according to the present invention is added, the freeze-thawing resistance is not reduced at all regardless of the combination of the water reducing agent.

이와 같은 사실은 프레쉬 콘크리트에 성분만을 첨가하여 얻은 콘크리트의 기포 조직에 있어서 기포 간격 계수 및 평균 기포 직경이 매우 크다는 사실에 의하여 명백하게 지지된다.This fact is clearly supported by the fact that the bubble spacing coefficient and the average bubble diameter are very large in the bubble structure of concrete obtained by adding only components to fresh concrete.

[실시예 1]Example 1

일반식(-1)의 화합물(여기서, R1및 R3는 각각 메틸이고, R2는 에틸렌이며, ℓ은 9임) 40중량부 및 일반식(-2)의 화합물(여기서, R4는 메틸임) 60중량부를 중합시켜 제조한 나트륨염 형태의 공중합체(분자량 : 약 20,000,40% 수용액의 점도 : 200cps)93중량부, 일반식(B)(여기서, R5는 스테아로일, R6는 수소, m은 35이고 n은 5임)의 화합물(분자량 : 약 2,500) 1중량부 및 에탄올아민염 형태의 일반식(C-2)(여기서, Rb 1및 Rb 2는 각각40 parts by weight of a compound of formula (-1), wherein R 1 and R 3 are each methyl, R 2 is ethylene, and l is 9; and a compound of formula (-2), wherein R 4 is Methyl) Copolymer in the form of sodium salt prepared by polymerization of 60 parts by weight (molecular weight: viscosity of about 20,000, 40% aqueous solution: 200 cps) 93 parts by weight, formula (B) (where R 5 is stearoyl, R 6 is hydrogen, m is 35 and n is 5 (molecular weight: about 2,500) 1 part by weight and general formula (C-2) in the form of ethanolamine salt, wherein R b 1 and R b 2 are each

Figure kpo00013
Figure kpo00013

이고, Rb 3는 히드록시임)의 화합물 및 에탄올아민염 형태의 일반식(C-2)(여기서, Rb 1은And R b 3 is hydroxy and a general formula (C-2) in the form of ethanolamine salt, wherein R b 1 is

Figure kpo00014
Figure kpo00014

이고, Rb 2및 Rb 3은 히드록시임)의 화합물 동량의 혼합물 6중량부로 구성된 콘크리트 혼화제.And R b 2 and R b 3 are hydroxy; and a concrete admixture composed of 6 parts by weight of a mixture of the same amount of the compound.

[실시예 2]Example 2

50ι 가경식 혼합기에 쇄석 955kg, 강모래 434kg 및 통상의 프틀랜드 시멘트 320kg을 채우고, 강모래 434kg을 더 채우고, 이 혼합물을 교반시켰다.A 50ι light mixer was charged with 955 kg of crushed stone, 434 kg of steel sand and 320 kg of conventional Pittland cement, and further with 434 kg of steel sand, and the mixture was stirred.

이어서, 여기에 실시예 1의 콘크리트 혼화제 470g이 융해된 물 171kg을 첨가하고, 혼합시켜 프레쉬 콘크리트를 얻었다.Subsequently, 171 kg of the water in which 470 g of the concrete admixture of Example 1 was melted was added and mixed to obtain fresh concrete.

Claims (4)

하기 일반식General formula
Figure kpo00015
Figure kpo00015
 (식중, R1은 수소 또는 메틸이고, R2는 저급(C2-C4)알킬렌이며, R3는 수소 또는 저급(C1-C5)알킬이고, ι는 정수 1-100임)의 화합물 10-95중량부 및 하기 일반식Wherein R 1 is hydrogen or methyl, R 2 is lower (C 2 -C 4 ) alkylene, R 3 is hydrogen or lower (C 1 -C 5 ) alkyl, ι is an integer 1-100) 10-95 parts by weight of a compound of the following general formula
Figure kpo00016
Figure kpo00016
 (식중, R4는 수소 또는 메틸임)의 화합물 또는 그의 염 90-5중량부를 중합시켜 제조한 공중합체로 되는 성분 90-95 중량부, 하기 일반식Wherein 90 to 95 parts by weight of a component of a copolymer prepared by polymerizing 90-5 parts by weight of a compound of formula (R 4 is hydrogen or methyl) or a salt thereof;
Figure kpo00017
Figure kpo00017
 (식중, R5는 수소 또는 알카노일이고, R6는 수소 또는 알킬이며, m은 정수 1-99이고 n은 정수 1-15이되 단, m+n이 정수 2-100이며Wherein R 5 is hydrogen or alkanoyl, R 6 is hydrogen or alkyl, m is an integer from 1-99 and n is an integer from 1-15, with m + n being an integer from 2-100
Figure kpo00018
Figure kpo00018
 단위가 임의로 나타남)의 화합물로 되는 B성분 0.05-5중량부 및 폴리옥시에틸렌 알킬 에테르 술페이트 또는 폴리옥시에틸렌 알킬페닐 에테르 술페이트 또는 그의 염, 폴리옥시에틸렌 알킬 에테르 포스페이트 또는 폴리옥시에틸렌 알킬페닐 에테르 포스페이트 또는 그의 염 및 알킬벤젠술폰산 또는 그의 염으로 되는 군 중에서 선택된 적어도 하나의 화합물로 되는 C성분 0.01-10중량부로 되는 콘크리트 혼화제.0.05-5 parts by weight of component B and polyoxyethylene alkyl ether sulfate or polyoxyethylene alkylphenyl ether sulfate or a salt thereof, polyoxyethylene alkyl ether phosphate or polyoxyethylene alkylphenyl ether A concrete admixture comprising 0.01-10 parts by weight of a C component comprising at least one compound selected from the group consisting of phosphates or salts thereof and alkylbenzenesulfonic acid or salts thereof. 제 1 항에 있어서, 하기 일반식According to claim 1, wherein the general formula
Figure kpo00019
Figure kpo00019
 의 화합물 10-95 중량부 및 하기 일반식10-95 parts by weight of a compound of the following general formula
Figure kpo00020
Figure kpo00020
 의 화합물 90-5중량부를 중합시켜 제조한 공중합체로 되는 나트륨염 형태의 성분 90-95중량부, 하기 일반식90-95 parts by weight of the component in the form of sodium salt which is a copolymer prepared by polymerizing 90-5 parts by weight of a compound of the following general formula
Figure kpo00021
Figure kpo00021
 (식중, R5는 스테아로일이고Wherein R 5 is stearoyl
Figure kpo00022
Figure kpo00022
 의 단위가 임의로 나타남)의 화합물로 되는 B성분 0.05-5중량부 및 에탄올아민염 형태의 하기 구조식0.05-5 parts by weight of component B and ethanolamine salt in the form of
Figure kpo00023
Figure kpo00023
 (식중, Rb 1및 Rb 2는 각각(Wherein R b 1 and R b 2 are each
Figure kpo00024
Figure kpo00024
 임)의 화합물 및 에탄올아민염 하기 구조식And a ethanolamine salt of the following structural formula
Figure kpo00025
Figure kpo00025
 (식중
Figure kpo00026
은(Meal
Figure kpo00026
silver
Figure kpo00027
Figure kpo00027
 임)의 화합물 동량의 혼합물로 되는 C성분 0.01-10 중량부로 되는 콘크리트 혼화제.A concrete admixture consisting of 0.01-10 parts by weight of C component which is a mixture of the same amount of the compound. 시멘트에 대하여 하기 일반식General formula for cement
Figure kpo00028
Figure kpo00028
 (식중, R1은 수소 또는 메틸이고, R2는 저급(C2-C4)알킬렌이며, R3는 수소 또는 저급(C1-C5)알킬이고, ℓ는 정수1-100임)의 화합물 10-95 중량부 및 하기 일반식Wherein R 1 is hydrogen or methyl, R 2 is lower (C 2 -C 4 ) alkylene, R 3 is hydrogen or lower (C 1 -C 5 ) alkyl, l is an integer from 1-100 10-95 parts by weight of a compound of the following general formula
Figure kpo00029
Figure kpo00029
 (식중, R4는 수소 또는 메틸임) 의 화합물 또는 그의 염 90-5중량부를 중합시켜 제조한 공중합체로 되는 성분 90-95중량부, 하기 일반식(Wherein R 4 is hydrogen or methyl) 90-95 parts by weight of a component consisting of a copolymer prepared by polymerizing 90-5 parts by weight of a compound or a salt thereof;
Figure kpo00030
Figure kpo00030
 (식중, R5는 수소 또는 알카노일이고, R6는 수소 또는 알킬이며, m은 정수 1-99이고 n은 정수 1-15이되 단, m+n이 정수 2-100이며Wherein R 5 is hydrogen or alkanoyl, R 6 is hydrogen or alkyl, m is an integer from 1-99 and n is an integer from 1-15, with m + n being an integer from 2-100
Figure kpo00031
Figure kpo00031
 단위가 임의로 나타남)의 화합물로 되는 B성분 0.05-5중량부 및 폴리옥시에틸렌 알킬 에테르 술페이트 또는 폴리옥시에틸렌 알킬페닐 에테르 술페이트 또는 그의 염, 폴리옥시에틸렌 알킬 에테르 포스페이트 또는 폴리옥시에틸렌 알킬페닐 에테르 포스페이트 또는 그의 염 및 알킬 벤젠술폰산 또는 그의 염으로 되는 군 중에서 선택된 적어도 하나의 화합물로 되는 C성분 0.01-10중량부로 되는 콘크리트 혼화제 0.001-1.0중량부를 첨가하는 것으로 되는 프레쉬 콘크리트의 제조 방법.0.05-5 parts by weight of component B and polyoxyethylene alkyl ether sulfate or polyoxyethylene alkylphenyl ether sulfate or a salt thereof, polyoxyethylene alkyl ether phosphate or polyoxyethylene alkylphenyl ether A method for producing fresh concrete comprising adding 0.001-1.0 parts by weight of a concrete admixture comprising 0.01-10 parts by weight of a C component comprising at least one compound selected from the group consisting of phosphates or salts thereof and alkyl benzenesulfonic acid or salts thereof. 제 3 항에 있어서, 콘크리트 혼화제가 하기 일반식4. The concrete admixture according to claim 3, wherein the concrete admixture is
Figure kpo00032
Figure kpo00032
 의 화합물 10-95중량부 및 하기 일반식10-95 parts by weight of a compound of the following general formula
Figure kpo00033
Figure kpo00033
 의 화합물 90-5중량부를 중합시켜 제조한 공중합체로 되는 나트륨염 형태의 성분 90-95중량부, 하기 일반식90-95 parts by weight of the component in the form of sodium salt which is a copolymer prepared by polymerizing 90-5 parts by weight of a compound of the following general formula
Figure kpo00034
Figure kpo00034
 (식중, R5는 스테아로일이고Wherein R 5 is stearoyl
Figure kpo00035
Figure kpo00035
 의 단위가 임의로 나타남)의 화합물로 되는 B성분 0.05-5중량부 및 에탄올아민염 형태의 하기 구조식0.05-5 parts by weight of component B and ethanolamine salt in the form of
Figure kpo00036
Figure kpo00036
 (식중, Rb 1및 Rb 2는 각각(Wherein R b 1 and R b 2 are each
Figure kpo00037
Figure kpo00037
 임)의 화합물 및 에탄올아민염 형태의 하기 구조식And the following structural formula in the form of the ethanolamine salt
Figure kpo00038
Figure kpo00038
 (식중 Rb 1은Where R b 1 is
Figure kpo00039
Figure kpo00039
 임)의 화합물 동량의 혼합물로 되는 C성분 0.01-10중량부로 되는 것인 방법.And 0.01-10 parts by weight of C component which is a mixture of the same amount of the compound.
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